Surface-active compositions having controlled foaming properties and process for controlling foam therewith

ABSTRACT

Surface-active compositions are provided having controlled foaming properties comprising an anionic sulphonate or sulphate ester surfactant, a nonionic polyoxyalkylene ether, ester or glycol surfactant, and an anionic polyoxyalkylene phosphate ester surfactant, the polyoxyalkylene phosphate ester and the polyoxyalkylene ether, ester or glycol surfactants serving as low foaming components, and the anionic surfactant increasing the foaming properties of such mixtures in proportion to the amount present. Adjuncts such as builders can also be present. A process for controlling the foaming properties of anionic sulphate or sulphonate ester surfactants and nonionic polyoxyalkylene ether, ester or glycol surfactants is provided, by combining therewith, in selected amounts, an anionic polyoxyalkylene phosphate ester surfactant to give any desired controlled low to high foaming properties.

0 United States Patent 11 1 1111 3,869,412

Waag 1 Mar. 4, 1975 [54] SURFACE-ACTIVE COMPOSITIONS 3,400,148 9/1965Quimby 252/89 V G CONTROLLED FOAMING 3,523,902 8/1970 Schmolka 252/559PROPERTIES AND PROCESS FOR FOREIGN PATENTS OR APPLICATIONS CONTROLLINGFOAM THEREWITH 1,119,884 6/1967 Great Britain 252/540 [76] lnventor: AkeWaag, Kattfotsvagen 3, OTHER PUBLICATIONS Stenungsund Sweden Soap andChemical Specialties, Phosphate [22] Filed: Dec. 20, 1971Surfactants-Properties and Uses, p. 55, 1962, May' h 1211 Appl. No.3210,161 ew Related US. Application Data Primary Examiner-John D. Welsh163] Continuation-impart of S61. NO. 648,248, June 23, 14mm"!EmmmerEdlth Rollins 1967. abandoned, and a continuation-in-part of Ser.No, 117,075, Feb. 19, 1971, Pat. No. 3,741,913, and [57] ABSTRACT 3 f f'ig' f i 9 1 1 3 g Surface-active compositions are provided having con-No t -1:11 A r11 1371; ;i l gzgla 0 trolled foaming propertiescomprising an anionic suli p phonate or sulphate ester surfactant, anonionic poly- [301 Foreign Application Priority Data oxyalkylene ether,ester or glycol surfactant, and an a anionic polyoxyalkylene phosphateester surfactant, June -3, 1966 SWC1I1 the p y y y phosphate ester andthe p y y Mar. 4, 1969 Sweden 2944/69 alkylene ether, ester or g ySurfactants Serving as I 10w foaming components, and the anionicsurfactant 152] 252/527 252/1316 252/89 increasing the foamingproperties of such mixtures in -52/321, 252/534, 252/540, 252 ortion tothe amount present. Adjuncts such as [51 Int. Cl. Clld 3/075, Cl 1d1/78, C1 1d l/83 builders can also be present [58 Field of Search252/527, 534, 546, 545, A f h f 252 559 540 321 52 35 89 DIG. 1 processOf COHH'O 1mg 11 e oammg PIOPGTUES Of amomc sulphate or sulphonate estersurfactants and [56] References Cited nonionic polyoxyalkylene ether,ester or glycol surfactants is provided, by combining therewith, in

UNlTED STATES PATENTS selected amounts, an anionic polyoxyalkylene I 5 5953 phosphate ester surfactant to give any desired ,Z ans1e I 3,294,69312/1966 Dupre et a1. 252/135 controlled low to foammg pmpertes'3.341.467 9/1967 Hwa 251/358 28 Claims, N0 Drawings SURFACE-ACTIVECOMPOSITIONS HAVING CONTROLLED FOAMING PROPERTIES AND PROCESS FORCONTROLLING FOAM THEREWITH This application is a continuation in part ofSer. No. 648,248 filed June 23, 1967 and now abandoned; Ser. No. 117,073filed Feb. 19, 1971, now US. Pat. No. 3,741,913, patented June 26, 1973;Ser. No. 16,250 filed Mar. 3. 1970, and Ser. No. 32,430, filed Apr. 27,1970, both now abandoned.

Many surfactants have a strong tendency to foam, particularly whensolutions thereof are agitated. Such foaming can produce seriousproblems, such as for example in automatic clothes and dishwashers, inchemical reactions, and in waste water treatment and sewage disposalplants. The problems arising from foam in waste waters being processedin water treatment plants is particularly irksome, and it is accentuatedin many cases because the washing detergent compositions used by thepublic have their natural foaming tendencies enhanced by the addition offoaming agents, to satisfy the housewives notion that the effectivenessof a washing solution is directly correlated with its tendency to foam.

The foaming tendencies of surfactants can be controlled in various ways,none fully satisfactory. Foam suppressing agents can be added, but thesefrequently have undesirable side effects. Typical foam-suppressingagents are silicones, fatty alcohols, oils, fats, waxes, and syntheticand natural resins. These, however, add to the cost of the product,because they serve as diluents, and have no surface activity, and cannotcontribute to the cleansing, emulsifying and wetting effect. ln use, inthe course of time. the surfactants may also solubilize thefoam-suppressing agent, and thereby destroy its foam suppressingeffectiveness. The foam-suppressing effect of these agents is alsorather unpredictable, according to the water in which the composition isused, and is not directly proportional to the amount used.

Surfactants vary considerably in their foaming properties. Generallyspeaking, nonionic surfactants tend to foam much less than anionicsurfactants, but combinations of nonionic and anionic surfactants mayfoam at least as much as the anionic surfactant, and in some cases maydisplay an enhanced foaming activity that is greater than either alone.Alkyl aryl sulphonates, for example. have a very high foaming power, andmixtures thereof with nonionic surfactants usually display an at leastequal foaming power, even when rather large amounts of the nonionicsurfactant are employed. Consequently. the foaming tendencies of anionicsurfactants combined with nonionic surfactants can present an evengreater problem. Similar problems are found with the alkyl sulphatesurfactants, and the aliphatic sulphonate and sulphate surfactants.

Some types of surfactants have a very low foaming power. Alkyl phosphateesters in which the alkyl group has from eight to twenty carbon atomsare described in French Pat. No. 1,454,195 as having the property ofsuppressing the foaming tendency of anionic surfactants such as alkylbenzene sulphonates. However, these phosphate esters are insolubilizedby the calcium and magnesium salts commonly found in hard water, andform precipitates. These are, therefore, very poor surfactant, cleansingand emulsifying agents.

Mayhew and Krupin, in an article entitled Phosphate Surfactants:Properties and Uses," Soap and Chemical Specialties April 1962, pages 55to 58, and 95, describe a series ofcomplex phosphate ester surfactantsin which the organic radical is an alkyl or alkylaryl oxyalkylene oxidecondensate. These compounds can have one or two such organic groups, andhave many of the properties of nonionic detergents, but are classitiedby Mayhew and Krupin as moderate foamers, foaming more than theirnonionic bases, but substantially less than the sulphated andsulphonated anionic surfactants. They are also said to have good surfacetension and wetting properties, although somewhat inferior to theirnonionic bases, but their cotton and hard surface detergency propertiesare comparable. Further information on these phosphate surfactants isgiven in US. Pat. No. 3,235,627 issued Feb. 16, 1966 to Mansfield, andUS. Pat No. 3,294,693, issued Dec. 27, 1966 to Dupre.

In accordance with the invention, surface-active compositions areprovided having controlled foaming properties, and comprising acombination of three surfactants, an anionic polyoxyalkylene ether,-ester or -glycol surfactant and a polyoxyalkylene phosphate estersurfactant. Combinations of the polyoxyalkylene ether, ester or -glycolsurfactant and polyoxyalkylene phosphate ester surfactant have very lowfoaming tendencies, and their foaming tendencies are increased by anydesired level by adding thereto an appropriate amount of the anionicsulphate or sulphonate surfactant. In addition to the surfactantcomponents, the compositions can contain organic and inorganic detergentbuilders, soil-suspending agents, and solvents usually employed inwashing and detergent compositions. The compositions of the inventionalso can be used as surface-active emulsifying agents, in which functionthey display a controlled foaming tendency.

The relative proportions ofthe anionic, nonionic and phosphatesurfactants can be widely varied, according to the foaming propertiesdesired. In general, however, the proportions of the three surfactantcomponents fall within the following ranges:

The polyoxyalkylene phosphate esters can be described by the followingformula:

R;0 to

R, and R can be the same or different. One or both of R, and R is aradical containing polyoxyalkylene ether and no more than one of R, andR is hydrogen.

The radical containing polyoxyalkylene ether is of the form in which nhas a value greater than 0, up to about 30. and preferably is within therange from about 1 to about l0, and denotes the average number ofoxyalkylene units in the chain. It will be understood that there will bepresent in admixture species having 11 values both higher and lower thanthe average value for n. R and R are hydrogen or methyl.

R is a primary or secondary straight or branched chain saturated orunsaturated aliphatic radical having from about to about 24 carbonatoms, preferably from about 12 to about 22 carbon atoms, or a mono-,di-, or tri-alkyl-substituted phenyl radical having from about 6 toabout 24 carbon atoms, and preferably from about 8 to about l8 carbonatoms in the alkyl portion.

M is hydrogen or a water-soluble salt-forming cation such as an alkalimetal, such as, for instance, sodium or potassium; ammonia; or anorganic amine, such as an alkanolamine or an alkylamine radical, forexample, monoethanolamine, diethanolamine, triethanolamine. butylamine,octylamine, or hexylamine.

These polyoxyalkylene phosphate esters are known compounds, and aredescribed in US. Pat. Nos. 3,294,693 and 3,235,627 and the disclosurethereof in these patents is hereby incorporated by reference. Additionalpolyoxyalkylene phosphate esters are described in US. Pat. No.3,400,148, at column 17, and in the Mayhew & Krupin article in Soup andSanitary Chemicals, referred to above. The disclosure thereof in thesepublications are also incorporated by reference.

Additional polyoxyalkylene phosphate ester surfactants are described inUS. Pat. No. 3,122,508 to Grifo. Mayhew, Stefcik and Woodward, datedFeb. 25, 1964, and in US. Pat, Nos. 3,004,056 and 3,004,057 to Nunn andHesse, dated Oct. 10, 1961.

In general, the polyoxyalkylene ether phosphates are prepared byreaction of phosphorous pentoxide, orthophosphoric acid, pyrophosphoricacid, or a polyphosphoric acid with a suitable nonionic surfactant base.

In the course of the esterification, monoesters and diesters may both beformed, but one may be obtained in preference to the other, according tothe reaction conditions and the molar proportions of the reactants.Phosphate esters composed of the mixtures of the monoand di-esters inany proportion can be employed, but it is generally preferred that themajor proportion, if not all, of the phosphate ester be composed ofmono-esters.

It may also be noted that the oxypropylene phosphate esters have alesser foaming tendency than the oxyethylene phosphate esters, and maybe preferred for low foaming compositions. Moremer, the lower the valueof n and the higher the number ofcarbon atoms in the R substituent ofthe oxyalkylene group, the less the foaming tendency ofthe phosphateester.

Exemplary organic compounds having an active hy drogen atom that can beemployed to produce alkylene oxide adducts for the radical of theoxyalkylene phosphate esters (R in the formula qRs are the primaryalcohols such as octanol, decanol, lauryl alcohol, myristyl alcohol,cetyl alcohol, stearyl alcohol, oleyl alcohol, eicosanol, docosanol,tetracosanol. straight or branched, primary or secondary OXO- alcohols,i.e., alcohols prepared by the OXO process, having from twelve totwenty-six carbon atoms, such as the essentially straight chain alcoholsproduced from Fischer-Tropsch olefins by the OXO-process, andmulti-branched chain alcohols produced from olefins hav ing at leastseven carbon atoms and two side chains, such as tripropylene,tetrapropylene, pentapropylene, diisobutylene and triisobutylene by theOXO process. monodi and trialkyl phenols, such as octyl phenol, isooctylphenol, nonyl phenol, dodecyl phenol, dioctyl phenol, dinonyl phenol,didodecyl phenol, trioctyl phenol, trihexyl phenol, tridodecyl phenol,methyloctyl phenol, and ethylisononyl phenol, tri-primary, secondary,and tertiary butyl phenol, 3-methyl-4,6-dibutyl phenol, octadecylphenol, di-octadecyl phenol, trioctadecyl phenol, mono-, diand tributylcresol. mono-, di-, and trinonyl cresol.

The polyoxyalkylene base can be polyoxy-l,2-propylene; polyoxyethylene;polyoxy-l,2-butylene; polyoxy-2,3-butylene; the socalled Pluronic typeof nonionic surfactants, generally block copolymers ofa polyoxyethylenechain and a polymerized alkylene oxide of at least three carbon atoms,preferably l,2-propylene oxide, ranging in molecular weight from about300 to about [0,000. Thus, the alkylene oxide condensate may consistentirely of one alkylene oxide, or of a condensed mixture of two or morealkylene oxides, such as a mixture of ethylene oxide and propyleneoxide, in blocks, or heterogeneously distributed in the oxyalkylenechain.

The anionic sulphate or sulphonate surfactant constitute a well knownclass of surfactants. The alkyl aryl sulfonates are defined by theformula where R is an alkyl radical from 8 to about 18 carbons, n is thenumber of radicals from one to three, and M is hydrogen or an alkalimetal, ammonium or organic amine cation. One example thereof is sodiumdodecyl benzene sulfonate.

Another example are the sulfonated phenyl polypropylene alkanes,characterized by the branched chain structure of polypropylene andtertiary alkyl carbon at the benzene ring, and having the followinggeneral structure:

i a e where M is hydrogen, an alkali metal, ammonium, or an organicamine cation, R and R are alkyl, of the type formula C,,H and at leastone R is a polypropylene group, the whole alkyl group containingpreferably l2 to [5 carbon atoms. These are known compounds, whosepreparation and properties are set forth in US. Pat. No. 2,477,383, toLewis, issued July 26, 1949; they are available in commerce under thetrade names "Oronite," "Ultrawet," and Neolene.

Other water-soluble alkyl aromatic sulfonic acids include those preparedby alkylating benzene or naphthalene with a kerosene fraction, followedby sulfonation to aromatic sulfonic acids, such as sodium keryl benzenesulfonate.

Other suitable anionic surfactants for controlling and adjusting thefoaming power to a desired level are the aliphatic hydrocarbonsulfonates, which have the general formula:

where R is a straight or branched, saturated or unsaturated hydrocarbonradical having from about 12 to about 23 carbon atoms, and M is analkali metal, ammonia or alkanolamine radical. Belonging to this groupare alkyl sulphonates based on the corresponding paraffins. petroleumsulfonates, and alkenyl sulphonates based on the correspondinga-olefins.

Further suitable anionic surfactants have the general formula:

where R is a straight or branched, saturated or unsaturated hydrocarbonradical having from about 8 to about 22 carbon atoms. or analkyl-substituted phenol having from about 8 to about 22 carbon atoms inits alkyl portion, a is a number from 1 to about 6, and M is an alkalimetal, ammonia or alkanolamine radical. Alcohols or phenols suitable asthe basis for these compounds are the alcohols and phenols mentionedhereinbefore. The sulphonates and sulphates indicated are prepared in amanner known per se by the use ofa sulphonating or sulphating agent,respectively, which is suitable for the type concerned.

Another class of useful surfactants are the amidoal kane sulfonates,which are characterized by the following structure:

where .4 is hydrogen or an alkali metal, i.e., ammo- 6 rine, NH CH CH SOH, and various N-substituted taurines, such as N-methyl taurine oraminopropane sulfonic acid, NH (CH SO H.

Other anionic surfactants include esters of sulfuric acid with aliphaticalcohols of about l0 to about 18 carbon atoms, particularly thosederived by reduction of oleic acid, tall oil, turkey red oil, and thefatty acids derived from coconut oil, palm oil, sperm oil, and the likelong-chain fatty acids, sulfonated castor oil, esters and ethers ofisethionic acid, long-chain fatty acid esters and long-chain alkylethers of 2,3-dihydroxypropane sulfonic acid, sulfuric acid esters ofmonoglycerides and glycerol monoesters, sulphosuccinates, naphthalenesulphonates, etc., as well as other types of surfactants such as soaps,alkylether carboxylic acids, alkyl betaines, alkyl sulphobetaines, aloneor in combination with each other. The anionic surfactants can be usedalone, as well as in admixture.

The nonionic surfactants which have been found to give a foam-reducingeffect in combination with the etherphosphate esters indicated are ofthe following formula:

where R is straight or branched, saturated or unsaturated, primary orsecondary alkyl radical having, in all, 8 to 26 carbon atoms, or a mono,di, or trialkylsubstituted phenol having from about 6 to about 24 carbonatoms in its alkyl portion, a is a number ranging from l to about 50,and l is hydrogen or the group (C;;H O),H. Where In is a number rangingfrom I about 10.

Exemplary organic compounds that can be employed to produce suchalkylene oxide adducts are the primary alcohols, such as octanol,decanol, lauryl alcohol, stearyl alcohol, oleyl alcohol, eicosanol,docosanol, tetracosanol, straight or branched, primary or secondaryOXOalcohols, i.e., alcohols prepared by the OXO process, having from 12to 26 carbon atoms, such as the essentially straight chain alcoholsproduced from Fischer-Tropsch olefins by the OXO-process, andmulti-branched chain alcohols produced from olefins hav ing at least 7carbon atoms and two side chains, such as tripropylene, tetrapropylene,pentapropylene, diisobutylene and triisobutylene by the OXO process,mono-, diand trialkyl phenols, such as octyl phenol, isooctyl phenol,nonyl phenol, dodecyl phenol, dioctyl phenol, dinonyl phenol, didodecylphenol, trioctyl phenol, trihexyl phenol, tridodecyl phenol, methyloctylphenol, and ethylisononyl phenol, tri-primary, secondary, andtertiarybutyl phenol, 3-methyl-4,6-dibutyl phenol, octadecyl phenol,di-octadecyl phenol, trioctadecyl phenol, mono-, diand tributyl cresol,mono, di-, and trinonyl cresol.

Further suitable nonionic surfactants have the general formula:

where m and M1 are numbers ranging from about 10 to about 50, and n, and11 are numbers ranging from 1 to about 50. Examples of surfactantsaccording to this formula are block copolymers of ethylene oxide andpropylene oxide based on propylene glycol and having added to thempropylene oxide up to a molecular weight of from about 1000 to about3000, after which ethylene oxide has been added to cause the proportionof ethylene oxide to constitute to 80% of the molecular weight of thecompound such as, for example, the compounds marketed by Wyandotte underthe trade name Pluronic.

The production of these nonionic compounds is carried out in a mannerknown per se at elevated temperature and pressure using an alkaline oracid catalyst by adding alkylene oxide to the corresponding alcohol oralkyl phenol.

In addition to the three surfactants, which are the essentialingredients ofthe compositions of the invention, the compositions caninclude other components which are customary in synthetic detergentformulations, such as inorganic and organic complex forming agents,neutral builder salts, soil suspending agents, optical brighteningagents, coloring agents and pigments, and perfumes.

lnorganic and organic chelating agents are added for softening hardwaters and for improving the soilremoval power ofthe detergent,particularly for heavily soiled articles. The amount of the alkalineinorganic complex forming agents is usually within the range from aboutID to about 80% by weight of the total solids ofthe composition,preferably from to 60% by weight, The alkali metal polyphosphates areparticularly advantageous in contributing heavy duty performance and inimproving detergent properties in hard water. Such polyphosphatesinclude pentasodium tripolyphosphate, sodium acid tripolyphosphate,pentapotassium tripolyphosphate, tetrasodium and tetrapotassiumpyrophosphate, sodium tetraphosphate, sodium hexametaphosphate, andpentaammonium tripolyphosphate. Also organic complex forming agentsofthe type aminopolycarboxylic acids, such as ethylenediaminetetraaceticacid, nitrilotriacetic acid and their alkaline salts are very usable.Still another type of advantageous complex forming agents are thepolyelectrolytes such as polyacrylates, polyitaconates and starchderivatives.

The alkali metal silicates, borates, and carbonates also can beemployed, alone or in admixture with polyphosphates as alkaline buildersalts. Examples are the sodium silicates, borax, and sodium carbonate.

Neutral builder salts such as sodium sulphate and potassium sulphate areformed in the neutralization of the sulphate or sulphonate esterdetergents and are usually present in admixture with such detergents.Additional amounts of such sulphates can be added, if desired, to buildor extend the composition.

Soil-suspending agents also can be added, particularly for heavy dutyformulations. Suitable soilsuspending agents are sodium carboxymethylcellulose, sodium cellulose sulphate, lower alkyl and hydroxy alkylcellulose ethers. such as ethyl hydroxyethyl cellulose. ethylhydroxypropyl cellulose, hydroxyethyl cellulose. methyl cellulose andhydroxypropyl cellulose, as well as polyvinyl alcohol andpolyvinylpyrrolidone. Soil suspending agents are usually used, if atall, in amounts of from about 0.05 to about 57r,' preferably from 0.1 to271, by weight of the total solids.

Optical brightening agents that may be used include stilbines,diamino-stilbines, acylated cyanuric and triazalyl derivatives ofstilbines, diphenyl derivatives, dibenzothiophene derivatives,aminocoumarone salts, derivatives of azotized amino-containingbenzoazoles, benzthiazoles, and benzimidazoles. A number of such agentsare disclosed in US Pat. No. 3,l22,508.

The compositions of the invention are useful as wetting agents,re-wetting agents, penetration agents, emulsifiers, leveling agents,dispersing agents, and washing and cleaning agents or detergents, in agreat variety of formulations, such as in cosmetics, adhesives,water-softening compositions, and detergent formulations.

The compositions of the invention can thus be used for washing andcleaning a variety of materials, such as textiles, metals, plastics,leather, wood, stone, glass, porcelain, painted surfaces, tile, both inhousehold and industrial applications. They can also be used for wettingor re-wetting and penetration, respectively, of materials such astextiles, metals, plastics, wax, wood. stone, paper, paints, lacquers,pigments, leather, cement, concrete, glass, porcelain, pulverulentchemical compounds and for emulsifying and dispersing solvents, oils,fats, waxes, tars, resins, plastics, softeners, biocides, bactericides,and fungicides, and also as a softener and anti-static agent fortextiles, paper, plas tics, materials, leather and the like. They alsoserve as emulsion-polymerization emulsifiers, emulsion breakers, foamcontrollers, for foamed rubber and foamed plastics, crystallizationmodifiers, resin removers in the cellulose and paper-making industry,and spinning adjuvants in the rayon industry.

The compositions of the invention for detergent use can be formulated assolutions or slurries which are spray-dried, or as light-duty orheavy-duty concentrated detergent solutions or concentrates. Thecompositions can also be formed into granules, flakes, chips andpowders, using conventional techniques, or plodded to form bars orcakes.

The following Examples in the opinion of the inveir tors representpreferred embodiments of the invention.

EXAMPLE 1 A series of 16 detergent formulations was prepared, having thefollowing composition, and differing only in the surfactant employed.The surfactants employed are listed in Table l.

The foaming properties of this formulation were tested in aqueoussolution containing 5 grams per liter of the composition. The height ofthe foam of the composition was measured in a mechanical foamingapparatus, in order to simulate the practical conditions under which thedetergent system was to be employed. The method employed is described inSeifen-Ole-Fette- Wasche, 1965, No.25, p. 913-917, Messmethode zurTestung gesteuerter Schaume".

The water used in the test was 5 of German hardness, and the washingtemperature was between 30 and C. The maximum foam height (in mm)obtained within this temperature range was noted, and is listed in TableI. In this test, a foam height of 200 mm or higher will cause anoverflow of foam in most types of washing machines. The maximum foamheight that can be produced in the test equipment is 400 mms.

TABLE 1 Component Parts by weight 4 5 Surfactant 700 MaX|ml 1m Sodiumtripolyphosphate 2000 Quantity foam height Sodium carbonate 500 .Nn.Surfactant mg/l (mms)' Sodium bicarbonate 250 Sodium sulphate 700 I 0-\Sulphate ester of tal- Sodium silicate 750 low fat y al h l Sodiumcarboxymethyl cellulose I00 adduct with 2 mols of E0 700 400 I B T ll'f'tt' l h l g fig 3 3:3, The foaming properties of th1s formulationwere of E0 700 200 tested in aqueous solution containing 5 grams perliter C 3232 35 1 5 of of the composition. The height of the foam of thecomadduct with 3,0 ts 15 position was measured in a mechanical foamingappaof P0 00 I0 ratus, in order to simulate the practical conditions J A500 400 under which the detergent system was to be employed.

B 200 The method employed as described in Seifen-Ole- 5 g 400Fette-Wasche, 1965, No. 25, p. 913-917, Messmeh A 200 400 thode ZurTestung gesteuerter Schaume.

B 500 The water used in the test was 5 of German hard- A 500 130 ness,and the washing temperature was between 30 0 c 300 and 90 C. The maximumfoam height (in mm) ob- 140 tained within this temperature range wasnoted, and is 9 A 200 '40 listed in Table I. In this test, a foam heightof 200 mm C 500 or higher will cause an overflow of foam in most types10 B 500 of washing machines. The maximum foam height that C 200 can beproduced in the test equipment is 400 mms. l l B 350 30 C 350 30 TABLEII l: B 200 30 C 500 Maximum Quantity foam height is A 600 2 B 50 200 NoSurfactant mg/l (mms) C 50 l o Dodec 'lb y enzene sul- H A 500 S phonate700 400 B 00 L0 2 E Tallow fatty alcohol C 00 adduct with 8 mols of A300 E0 700 200 B 200 100 3 F Phosphate ester of cetyl C 200 alcoholadduct with A 100 40 2 mols of PO 700 10 B 300 50 C 300 4 D 500 400 E200 H) ethylene nude. P0 l.Z- propylene oxide 5 D 350 400 1 Jill) mmfoam mcrfoaming E 350 6 D 200 400 v E 500 It is apparent from the datafor No. 1 that the anionic tallow polyoxyethylene sulphate estersurfactant gives 7 g :88 200 a very high foam volume and this cannot becontrolled 3 D 350 3 0 by mixing it either with the nonionic tallowpolyoxyeth- 9 g 288 700 ylene glycol surfactant (Nos. 4 to 6) or withthe stearyl E 5 polyoxypropylene phosphate ester (Nos. 7 to 9). The 10 E500 I0 nonionic surfactant and phosphate ester together (Nos. F 200 10to 12) are too low foaming to be acceptable for most 11 E 0 purposes.However, when all three surfactants are com- 13 E 6 m bined (Nos. 13 to16) then the foaming properties of F 500 the composition are in directproportion to the amount 13 D 600 of alkylether sulphate. and byadjusting the proportion E 50 l80 of the alkylether sulphate. it ispossible to obtain any 4 g 68 desired foam volume. It is apparent thatthe ratio ofthe E 15 140 nonionic surfactant to the alkylether phosphateester 5 g may be varied without affecting the foam volume. 5 5 60 F 250EXAMPLE 2 16 D 100 I E 300 20 A series of sixteen detergent formulationswas pre- F 300 pared. having the following composition, and differingonly in the surfactant employed. The surfactants employed are listed inTable I.

- E0 ethylene oxide. P0 1.2- propylene oxide. 400 mm foam overfonming Itis apparent from the data in No. I that the anionic dodecyl benzenesulphonate surfactant has a very high foam volume and that this cannotbe reduced (Nos. 4 to 6) by adding a nonionic tallow polyoxyethyleneglycol surfactant (Nos. 7 to 9) or stearyl polyoxyethylene phosphateester to it. The combinations of nonionic surfactant and phoshpate ester(Nos. to 12) is too low foaming to be acceptable for most purposes.When. however. all three surfactants are combined (Nos. 13 to 16 then.the foam volume obtained is in direct proportion to the amount ofalkylaryl sulphonate. and is not varied by varying the relativeproportions of nonionic surfactant and alkylether phosphate ester.

EXAMPLE 3 A series of 16 detergent formulations was prepared, having thefollowing composition. and differing only in the surfactant employed.The surfactants employed are listed in Table 1.

The foaming properties of this formulation were tested in aqueoussolution containing 5 grams per liter of the composition. The height ofthe foam of the composition was measured in a mechanical foamingapparatus. in order to simulate the practical conditions under which thedetergent system was to be employed. The method employed is described inSeifen-leFette- Wasche. 1965. No. 25. p. 913-917. Messmethode zurTestung gesteuerter Schiiume".

The water used in the test was 5 of German hardness. and the washingtemperature was between and 90C. The maximum foam height (in mm)obtained within this temperature range was noted. and is listed in TableIII. In this test. a foam height of 200 mm or higher will cause anoverflow of foam in most types of washing machines.

Maximum foam height (nuns)- Quantity Surfactant mg/I SUI) 200 350 350200 500 E0 ethylene UML|. P0 1.2 propylene oxide. 400 mm foamo\erfoaming It is apparent from No. 1 that the anionic pentadecylene tooctadecylene sulphonate surfactant has a very high foam volume. and thiscannot be reduced appreciably by combining it with the nonionic tallowpolyoxyethylene glycol surfactant (Nos. 4 to 6) or with the tallowpolyoxyethylene phosphate ester surfactant (Nos. 7 to 9). Thecombination of nonionic surfactant and phosphate ester (Nos. 10 to 12)is too low foaming to be acceptable for most purposes. When. however.all three surfactants are combined (Nos. 13 to 15). then the foam volumeis in direct proportion to the amount of olefin sulphonate. and therelative proportions of nonionic surfactant and the phosphate ester canbe varied without affecting foam volume.

EXAMPLE 4 A series of 16 detergent formulations was prepared. having thefollowing composition. and differing only in the surfactant employed.The surfactants employed are listed in Table IV.

The foaming properties of this formulation were tested in aqueoussolution containing 5 grams per liter of the composition. The height ofthe foam ofthe composition was measured in a mechanical foamingapparatus, in order to simulate the practical conditions under which thedetergent system was to be employed The method employed is described inSeifen-Ole-Fette- Wasche. 1965. No. 25. p. 913-917. Messmethode zurTestung gesteuerter Sch'riume."

The water used in the test was 5 of German hardness. and the washingtemperature was between 30 and C. The maximum foam height (in mm)obtained within this temperature range was noted. and is listed in TableIV. In this test. a foam height of 200 mm or higher will cause anoverflow of foam in most types of washing machines.

TABLE IV Component Parts by weight Surfactant 70 Maxlmllm Sodiumtripolyphosphate 50 Quantity foam h! Trisodium nitrilotriacetic acid1000 NO. surfdclflm mg/l (mms)' Sodium carbonate 50 Sodium bicarbonate25 l A Sulphate ester of tal- Sodium sulphate 70 low fatty alcoholSodium silicate 75 adduct with 2 mols of 10 Sodium carboxymethylcellulose 10 E 700 400 2 B Tallow fatty alcohol adduct with 8 mols of700 200 The foaming properties of this formulation were 3 C l hosplhaieehsnlar of tested in aqueous solution containing grams per liter g molsof the composition. The height of the foam of the comof PO 700 10position was measured in a mechanical foaming apparatus, in order tosimulate the practical conditions 4 A 500 400 B 200 under WhlCh thedetergent system was to be employed. 5 A 350 400 The method employed isdescribed in Seifen-Ole-Fetteb 2 338 400 Wasche, 1965, N0. 25, p.913-917, Messmethode Zur B 5 0 Testung gesteuerter Schaume. 7 500 M0 Thewater used in the test was 5 of German hard- 2 200 ness, and the washingtemperature was between 30 it A 350 140 and 90 C. The maximum foamheight (in mm) ob- 9 g 140 tained within this temperature range wasnoted, and is C 5 listed in Table V. In this test, a foam height of 200mm 0 3 or higher will cause an overflow of foam in most types [U B 50 0C 200 of washing machines. I l B 350 C 350 30 TABLE V I: B 200 C 500 30Maximum Quantity foam height I 3 A 600 No. Surfactant mg/l (mms) B 50200 C 50 l A Sodium dodecyl benzene 14 A 500 sulphonate 700 400 B I00I50 2 B Tallow fatty alcohol C 100 adduct with 8 mols l 5 A 300 of E0700 200 B 200 I00 3 C Phosphate ester of cetyl C 100 alcohol adduct withlo A 100 2 mols of POI 700 10 B 300 C 300 4 A 500 400 B 200 E0 ethyleneoudc. P0 LZ-propylene oxide 5 g 400 1 400 mm foam merfoaniing 6 A 00 4005 B 500 It is apparent from the data for No. 1 that the anionic 7 A 500200 tallow polyoxyethylene sulphate surfactant gives a very C 200 highfoam volume and this cannot be controlled by 8 A 350 200 mixing iteither with the nonionic tallow polyoxyethyl- 9 g 388 200 ene glycolsurfactant (Nos. 4 to 6) or with the stearyl 50 C 500 polyoxypropylenephosphate ester (Nos. 7 to 9). The 10 B 500 I0 nonionic surfactant andphosphate ester together (Nos. 7 100 10 to 12 are too low foaming to beacceptable for most g purposes. However. when all three surfactants arecom- 13 B 6 10 bined (Nos. l3 to l6), then the foaming properties of C500 the composition are in direct proportion to the amount 13 A 600 ofalkylether sulphate, and by adjusting the proportion g .20 180 of thealkylether sulphate, it is possible to obtain any 4 A 8 desired foamvolume. It is apparent that the ratio ofthe B 150 140 nonionicsurfactant to the alkylether phosphate ester 15 g may be varied withoutaffecting the foam volume. B 350 (,0

C 250 EXAMPLE 5 16 A 100 l B 300 20 A series of l6 detergentformulations was prepared, C 300 having the following composition, anddiffering only in the surfactant employed. The surfactants employed arelisted in Table V.

" E0 ethylene oxide. P0 l,2-propylene oxide 400 mm foam overfoaming Itis apparent from the data for No. 1 that the anionic sodium dodecylbenzene sulphate surfactant gives a very high volume and this cannot becontrolled by mixing it either with the nonionic tallow polyoxyethyleneglycol surfactant (Nos. 4 to 6) or with the cetyl poly oxypropylenephosphate ester (Nos. 7 to 9). The nonionic surfactant and phosphateester together (Nos. 10 to 12) are too low foaming to be acceptable formost purposes. However, when all three surfactants are combined (Nos. 13to 16), then the foaming properties of the composition are in directproportion to the amount of dodecyl benzene sulphonate and by adjustingthe proportion of the dodecyl benzene sulphonate. it is possible toobtain any desired foam volume. lt is apparent that the ratio of thenonionic surfactant to the alkylether phosphate ester may be variedwithout affecting the foam volume.

EXAMPLE 6 A series of 16 detergent formulations was prepared. having thefollowing composition. and differing only in the surfactant employed.The surfactants employed are listed in Table VI.

The foaming properties of this formulation were tested in aqueoussolution containing 5 grams per liter of the composition. The height ofthe foam of the composition was measured in a mechanical foamingapparatus. in order to simulate the practical conditions under which thedetergent system was to be employed. The method employed is described inSeifen-Ole-Fette- Wasc/ie. 1965, No. 25. p. 913-917. Messmethode zurTestung gesteuerter Schaume.

The water used in the test was 5 of German hardness, and the washingtemperature was between 30 and 90 C. The maximum foam height (in mm)obtained within this temperature range was noted. and is listed in TableVI. In this test, a foam height of 200 mm or higher will cause anoverflow of foam in most types of washing machines.

TABLE Vl-Continued Maximum foam hci 'ht tmnis Quantity mg/l SurfactantIOU E0 ethylene oxide. P0 l propylene o\ide 400 mm foam murfoaming lt isapparent from No. l that the anionic pentadecylene to octadecylenesulphonate surfactant tant has a very high foam volume. and this cannotbe reduced appreciably by combining it with the nonionic tallowpolyoxyethylene glycol surfactant (Nos. 4 to 6) or with the tallowpolyoxyethylene phosphate ester surfactant (Nos. 7 to 9). Thecombination of nonionic surfactant and phosphate ester (Nos. 10 to 12)is too low foaming to be acceptable for most purposes. When. however.all three surfactants are combined (Nos. 13 to l5), then the foam volumeis in direct proportion to the amount of olefin sulphonate. and therelative proportions of nonionic surfactant and the phosphate ester canbe varied without affecting foam volume.

EXAMPLE 7 A series of l6 detergent formulations was prepared. having thefollowing composition, and differing only in the surfactant employed.The surfactants employed are listed in Table VI].

Component Parts by weight Surfactant 700 Sodium tripolyphosphate 3000Sodium carbonate (calcined) 300 Trisodium phosphate Sodium metasilicate300 The foaming properties of this formulation were tested in aqueoussolution containing 5 grants per liter of the composition. The heightofthe foam of the composition was measured in a mechanical foaming apparatus. in order to simulate the practical conditions under which thedetergent system was to be employed. The method employed is described inSeifen-Ole-Fette- Wasche. I965. No. 25. p. 913-917. Messmethode zurTestung gesteuerter Schiiume.

The water used in the test was 5 of German hardness. and the washingtemperature was between 30 and C. The maximum foam height (in mm)obtained within this temperature range was noted. and is listed in TableVll. In this test. a foam height of 200 mm or higher will cause anoverflow of foam in most types of washing machines. The maximum foamheight that can be produced in the test equipment is 400 mms.

TABLE VII Maximum Quantity foam height No. Surfactant mg/l (mms) l ASodium dodecyl benzene sulfonate 700 400 2 B Nonyl phenol adduct withIt) mols of E 700 200 l C Phosphate ester of stearyl alcohol adduct with8.5 mols of PO 700 B 200 i A 350 400 B 350 h A 200 400 C 200 K A 350 400C 350 u A 200 400 ll! B 500 50 C 200 l l B 350 50 C 350 12 B 200 C 500 B100 190 C I00 N A 300 B 200 160 C 200 F A 200 B 200 150 C 300 to A 100 BI00 I00 C 500 H) ethylene nude. P0 l,2-propylene oxide 4011 min foaminerfoaniing It is apparent from the data for No. I that the anionicsodium dodecyl benzene sulphonate surfactant gives a very high foamvolume and this cannot be controlled by mixing it either with thenonionic nonyl phenol polyoxycthylene glycol ether surfactant (Nos 4 to6) or with the stearyl polyoxypropylene phosphate ester (Nos. 7' to 9The nonionic surfactant and phosphate ester together (Nos. 10 to 12) aretoo low foaming to be acceptable for most purposes. However, when allthree surfactants are combined (Nos. 13 to 16), then the foamingproperties of the composition are in direct proportion to the amount ofalkylether sulphate, and by adjusting the proportion of the alkylethersulphate, it is possible to obtain any desired foam volume. It isapparent that the ratio of the nonionic surfactant to the alkyletherphosphate ester may be varied without affecting the foam volume.

EXAMPLE 8 A series of 16 detergent formulations was prepared, having thefollowing composition. and differing only in the surfactant employed.The surfactants employed are listed in Table VIII.

Component Parts by weight Surfactant 10 Sodium carbonate (calcined) 100The foaming properties of this formulation were tested in aqueoussolution containingl 1 grams per liter of the composition. The height ofthe foam of the composition was measured in a mechanical foamingapparatus, in order to simulate the practical conditions under which thedetergent system was to be employed. The method employed is described inSeifen-Ole-Fette- Wasche, 1965, No. 25, p. 913-917, Messmethode zurTestung gesteuerter Schaume".

The water used in the test was 5 of hardness, and the washingtemperature was between 30 and C. The maximum foam height (in mm)obtained within this temperature range was noted, and is listed in TableVIII. In this test, a foam height of 200 mm or higher will cause anoverflow of foam in most types ofwashing machines.

TABLE VIII Maximum Quantity foamheight No. Surfactant m g/ l (mnis l ASulphate ester of n-primary Cut-Cg fatty alcohol adduct with 3 mols ofE0 500 400 2 B n-Primary C -C fatty alcohol adduct with 30 mols of E0500 250 l C Phosphate ester of n-primary C -C alcohol adduct with 3 molsof E0 00 20 B I00 5 A 250 400 II) B 400 40 C I00 I l B 30 C 250 II B I0030 B 50 I80 C 5O 14 A 300 B 100 I50 C I00 15 A 200 B 150 I00 C I50 16 A100 E0 ethylene oxide. P0 l.Z-propylene oxide 400 mm foam overfoaming Itis apparent from the data for No. I that the anionic C, ,-C alcoholpolyoxyethylene sulphate ester surfactant gives a very high foam volumeand this cannot be controlled by mixing it either with the nonionicCut-C20 alcohol polyoxyethylene glycol surfactant (Nos. 4 to 6) or withthe C ,C alcohol polyoxyethylene phosphate ester (Nos. 7 to 9). Thenonionic surfactant and phosphate ester together (Nos. to 12) are toolow foaming to be acceptable for most purposes. However. when all threesurfactants are combined (Nos. l3 to l6). then the foaming properties ofthe composition are in direct proportion to the amount of alkylethersulphate, and by adjusting the proportion of the alkylether sulphate. itis possible to obtain any desired foam volume. It is apparent that theratio of the nonionic surfactant to the alkylether phosphate ester maybe varied without affecting the foam volume.

EXAMPLE 9 A series of 16 detergent formulations was prepared. having thefollowing composition. and differing only in the surfactant employed.The surfactants employed are listed in Table lX.

The foaming properties of this formulation were tested in aqueoussolution containing 0.5 gram per liter of the composition. The height ofthe foam of the composition was measured in a mechanical foamingapparatus. in order to simulate the practical conditions under which thedetergent system was to be employed. The method employed is described inSeifen-Ole-Fette- Wasche. 1965, No. 25. p. 913-917. Messmethode zurTestung gesteuerter Schaume".

The water used in the test was 5 of German hardness. and the washingtemperature was between and 90 C. The maximum foam height (in mm)obtained within this temperature range was noted, and is listed in TableIX. In this test. a foam height of 200 mm or higher will cause anoverflow of foam in most types of washing machines.

TABLE lX-Continued Maximum foam height (mmsl' Quantity Surfactant mg/]IOU lUU

E0 ethylene oxide. P0 L1 propylene oxide 400 mm foam o\ erfuamtng It isapparent from the date for No. 1 that the anionic di-C,-;C alcoholsulphosuccinate surfactant gives a very high foam volume and this cannotbe controlled by mixing it either with the nonionic tridecylpolyoxyethylene glycol surfactant (Nos. 4 to 6) or with the laurylpolyoxyethylene phosphate ester (Nos. 7 to 9). The nonionic surfactantand phosphate ester together (Nos. 10 to 12) are too low foaming to beacceptable for a lot of purposes. However. when all three surfactantsare combined (Nos. 13 to 16). then the foaming properties of thecomposition are in direct proportion to the amount of alkyl sulphate.and by adjusting the proportion ofthe alkyl sulphate, it is possible toobtain any desired foam volume. It is apparent that the ratio of thenonionic surfactant to the alkylether phosphate ester may be variedwithout affecting the foam volume.

EXAMPLE 10 Vinyl chloride was polymerized to form polyvinyl chloride inphosphorylated presence of potassium persulphate as a catalyst. and 3%surfactant as an emulsifier. The polymer emulsion that was formed had asolids content of 40%. The surfactant composition was composed of amixture of 60% lauryl sulphate, 20% ethylene oxide-propylene oxide blockcopolymer in which the proportion of the ethylene oxide was 20%, and themolecular weight of the propylene oxide com ponent was 1850. and 20% ofan alkylether phosphate ester based on nonyl phenol condensed with 10mols of ethylene oxide and phsphorylated by reaction with phosphorouspentoxide.

Foam testing by shaking cylinders half filled with the polymer emulsionshowed that the foaming properties were very low or 10 ml and that it ispossible to control the foaming by varying the relative proportions ofthe surfactants. in the manner illustrated in Example 1.

Having regard to the foregoing disclosures. the following is claimed asthe inventive. and patentable embodiments thereof:

1. A surface-active composition having controlled foaming properties.and consisting essentially of. in combination. a surfactant selectedfrom the group consisting of anionic sulphonate and sulphatesurfactants. a nonionic surfactant selected from the group consisting ofpolyoxyalkylene ether. -ester and -glycol surfactants. and apolyoxyalkylene phosphate ester surfao /1 by weight Anionic sulphate orsulphonate surfactant l 95 Nonionic Polyoxyalkylene ether. -ester orglycol surfactant l 95 Polyoxyalkylene phosphate ester surfactant 1 95the polyoxyalkylene phosphate ester having the formula:

wherein R. and R are selected from hydrogen and polyoxyalkylene etherradicals, and no more than one of R, and R is hydrogen, thepolyoxyalkylene ether radical being of the form wherein a has a valuegreater than zero up to about 30, and denotes the average number ofoxyalkylene units in the chain. R, and R are hydrogen or methyl, and Ris a primary or secondary straight or branched chain saturated orunsaturated radical having from about lO to about 24 carbon atoms, or amono-, di-, or trialkylsubstituted phenyl radical having from about 6 toabout 24 carbon atoms; and M is hydrogen or a water-soluble salt-formingcation.

2. A composition according to claim 1 including, in addition. achelating agent selected from the group consisting of inorganicchelating agents and organic chelating agents selected fromaminopolycarboxylic acids and polyelectrolytes selected from the groupconsisting of polyacrylates, polyitaconates, and starch derivathes, inan amount within the range from about lO to about 80".? by weight of thetotal solids of the composition.

3. A composition according to claim 1 including, in addition. asoil-suspending agent. in an amount within the range from about 0.05 toabout 5% by weight of the total solids of the composition.

4. A composition according to claim 1, in which the relative proportionsof the anionic. nonionic and phos phate surfactants fall within thefollowing ranges:

d by weight Anionic sulphate or sul- [l 95] It) 9t) -Continued /1 byweight phonate surfactant Nonionic polyoxyalkylene ether, -ester or-glycol [l IO 9t) surfactant Polyoxyalkylene phosphate ester surfactant[1 95] l0 90.

5. A composition according to claim 1 in which any one of R, and R inthe polyoxyalkylene ether radical is methyl and the other is hydrogen.

6. A composition according to claim 1 in which the anionic sulphonatesurfactant is an alkyl aryl sulfonate having the formula where R isalkyl having from 8 to about 18 carbons, n is a number from one tothree, and M is hydrogen or an alkali metal, ammonium or organic aminecation.

7. A composition according to claim 1 in which the anionic sulphonatesurfactant is an am idoalkane sulfonate, having the structure:

R-C0-N -(Cllg) S03A where A is hydrogen or an alkali metal or aluminum,n is a small whole number from l to about 5, R is hydrogen or an alkyl,aryl, or cycloaliphatic group, and R is an alkyl or alkylene radical.

8. A composition according to claim 1 in which the anionic surfactant isan ester of sulfuric acid with an aliphatic alcohol of from 10 to 18carbon atoms.

9. A composition according to claim 1 in which the anionic surfactant isa sulfonate having the following general formula:

where R is a straight or branched, saturated or unsaturated hydrocarbonradical having l2 to 22 carbon atoms, or an alkyl benzene having astraight or branched alkyl containing 12 to 18 carbon atoms, X is analkali metal, ammonia or alkanolamine-radical.

10. A composition according to claim 1 in which the anionic surfactantis a sulfated alkoxylate having the following general formula:

where R is a straight or branched, saturated or unsaturated hydrocarbonradical having 8 to 22 carbon atoms, or an alkyl-substituted phenolhaving 8 to 18 carbon atoms in its alkyl portion, n is a number rangingbetween 0 and 6, and X is an alkali metal, ammonia or alkanolamineradical.

11. A composition according to claim 1 in which the nonionic surfactanthas the following general formula:

where R is a straight or branched, saturated or unsaturated primary orsecondary alkyl radical having. in all, 8 to 26 carbon atoms, or amono-, dior trialkylsubstituted phenol having. in all, 6 to 24 carbonatoms in its alkyl portion, :1 is a number ranging from 1 to 50 and Y ishydrogen or the group -(C H O),,,H, where m is a number ranging from 1to 10.

12. A composition according to claim 1 in which the nonionic surfactanthas the following general formula:

where m, and m are numbers ranging from to 50. and n, and n are numbersranging from 1 to 50.

13. A composition according to claim 1 including, in addition, an alkalimetal polyphosphate in an amount within the range from about 10% toabout 80% by weight of the total solids of the composition.

14. A composition according to claim 1 including, in addition, asoil-suspending agent in an amount of from about 0.05% to about 571, byweight ofthe total solids. selected from alkali metal carboxymethylcellulose, alkali metal cellulose sulphate, and lower alkyl andhydroxyalkyl cellulose ethers.

15. A composition according to claim 1, consisting essentially of 70parts by weight of surfactants. 50 parts by weight sodiumtripolyphosphate, 50 parts by weight sodium carbonate, parts by weightsodium bicarbonate, 70 parts by weight sodium sulphate. 75 parts byweight sodium silicate, and 10 parts by weight sodium carboxymethylcellulose.

16. A composition according to claim 1, including in addition, an amountwithin the range from about 10% to about 807: by weight of the totalsolids of the com position of an organic chelating agent selected fromaminopolycarboxylic acids and polyelectrolytes selected from the groupconsisting of polyacrylates. polyitaconates, and starch derivatives.

17. A composition according to claim 14, in which the surfactants aresulphate ester oftallow fatty alcohol adduct with 2 mols of ethyleneoxide. tallow fatty alcohol adduct with 8 mols ofethylene oxide andphosphate ester of stearyl alcohol adduct with 2.0 mols of 1.2-propylene oxide.

18. A composition according to claim 15. in which the surfactants aredodecylbenzene sulphonate, tallow fatty alcohol adduct with 8 mols ofethylene oxide and phosphate ester of cetyl alcohol adduct with 2 molsof 1,2-propylene oxide.

19. A composition according to claim 15, in which the surfactants ares-C olefin sulphonate, tallow fatty alcohol adduct with 8 mols ofethylene oxide and phosphate ester of tallow fatty alcohol adduct withl2 mols of ethylene oxide.

20. A composition according to claim 15, in which the surfactants aresulphate ester of n-primary -C fatty alcohol and -C alcoholsulphosuccinate (lzl tridecyl alcohol adduct with 8 mols of ethyleneoxide and phosphate ester oflauryl alcohol adduct with 2 mols ofethylene oxide.

21. A composition according to claim 1, consisting essentially of partsby weight of surfactants, 50 parts by weight sodium tripolyphosphate,100 parts by weight trisodium nitrilotriacetic acid, 50 parts by weightsodium carbonate, 25 parts by weight sodium bicarbonate, 70 parts byweight sodium sulphate, parts by weight sodium silicate, and 10 parts byweight sodium carboxymethyl cellulose.

22. A composition according to claim 21, in which the surfactants aresulphate ester of tallow fatty alcohol adduct with 2 mols of ethyleneoxide, tallow fatty alcohol adduct with 8 mols ofethylene oxide andphosphate ester of stearyl alcohol adduct with 2 mols of l,2- propyleneoxide.

23. A composition according to claim 21, in which the surfactants aresodium dodecyl benzene sulphonate, tallow fatty alcohol adduct with 8mols of ethylene oxide. and phosphate ester of cetyl alcohol adduct with2 mols of LIZ-propylene oxide.

24. A composition according to claim 21, in which the surfactants are C5C olefin sulphonate, tallow fatty alcohol adduct with 8 mols ofethylene oxide and phosphate ester of tallow fatty alcohol adduct with1.2 mols of ethylene oxide.

25. A composition according to claim 1, consisting essentially of 70parts by weight of surfactants. 300 parts by weight sodiumtripolyphosphate. 30 parts by weight sodium carbonate (calcined), 5parts by weight trisodium phosphate. and 30 parts by weight sodiummetasilicate.

26. A composition according to claim 25in which the surfactants aresodium dodecyl benzene sulfonate. nonyl phenol adduct with 10 mols ofethylene oxide and phosphate ester of stearyl alcohol adduct with 8.5mols of 1.2- propylene oxide.

27. A composition according to claim 1 consisting essentially of, inaddition to the surfactant, sodium carbonate (calcined).

28. A composition according to claim 27, in which the surfactants aresulphate ester of n-primary C .;-C fatty alcohol adduct with 3 mols ofethylene oxide, nprimary C|.,C fatty alcohol adduct with 30 mols ofethylene oxide, and phosphate ester of n-primary (gm-C alcohol adductwith 3 mols of ethylene oxide,

Page 1 of 2 UNITED STATES PATENT OFFICE Inventor(s) Dated March 4 1975Ake W aag It is eertified that error appears in the above-identifiedpatent and that sald Letters Patent are hereby corrected as shown below:

Column 4, line 51 6 Column 6, line 58 following "radical" add having 2 4n 3 )m Z-3 4 I ARQ QR shouldb'e Column 2 line 19 Column 10 Table II,

Ijo. 9, line 50, column 4 Qolumn 17, l'1ne 30,

last column maximum foam highi) Qelumn 20, line 42 line 2 Column 21,line 65 to Celumn 22, line "735?; column of Table.

,laim 4 before "presence" add 7 "as" should be --is "200" should be oadd omit "phosphorylated and insert th .1;

"phsphorylated" should be phosphoryleted I omit 1 each occurrence O I II Page 2 of 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Qpaten m mfiml Dated r h 97 Inven tor(s) Ake Waag It is certified thaterror appears in the above:ldentifiedpatent and that said Letters Patentare hereby corrected as shown below: 7

Qolumn 23, line 7 v I FEE-l2 H 2 4)1 3 6)m'" 2 s 4- 0 I 3 6 2 )n"'"should be 0 v I Signed and Sealed tl u's sixteenth Day Of March 1976[SEAL] Attest:

RUTH C. M AHSON C. MARSHALL DANN Alffl'flllg Officer Commissioneroj'Patents and Trademarks

1. A SURFACE-ACTIVE COMPOSITION HAVING CONTROLLED FOAMING PROPERTIES,ANS CONSISTING ESSENTIALLY OF, IN COMBINATION, A SURFACTANT SELECTEDFROM THE GROUP CONSISTING OF ANIONIC SULPHONATE AND SULPHATESURFACTANTS, A NONIONIC SURFACTANT SULLECTED FROM THE GROUP CONSISTINGOF POLYOXYALKYLENE ETHER, ESTER AND-GLYCOL SURFACTANTS, AND APOLYOXYALKYLENE PHOSPHATE ESTER SURFACTANT, THE COMBINATION OF THEPOLYOXYALKYLENE ETHER, -ESTER OR GLYCOL SURFACTANT AND POLYOXYALKYLENEPHOSPHATE ESTER SURFACTANT HAVING A LOW FOAMING PROPERTY WHICH ISCONTROLLABLY INCREASED BY THE PROPORTION OF ANIONIC SULPHATE ORSULPHONATE SURFACTANT, THE RELATIVE PROPORTIONS OF THE ANIONIC, NONIONICAND PHOSPHATE SURFACTANTS FALLING WITHIN THE RANGES:
 2. A compositionaccording to claim 1 including, in addition, a chelating agent selectedfrom the group consisting of inorganic chelating agents and organicchelating agents selected from aminopolycarboxylic acids andpolyelectrolytes selected from the group consisting of polyacrylates,polyitaconates, and starch derivatives, in an amount within the rangefrom about 10 to about 80% by weight of the total solids of thecomposition.
 3. A composition according to claim 1 including, inaddition, a soil-suspending agent, in an amount within the range fromabout 0.05 to about 5% by weight of the total solids of the composition.4. A composition according to claim 1, in which the relative proportionsof the anionic, nonionic and phosphate surfactants fall within thefollowing ranges:
 5. A composition according to claim 1 in which any oneof R4 and R5 in the polyoxyalkylene ether radical is methyl and theother is hydrogen.
 6. A composition according to claim 1 in which theanionic sulphonate surfactant is an alkyl aryl sulfonate having theformula
 7. A composition according to claim 1 in which the anionicsulphonate surfactant is an amidoalkane sulfonate, having the structure:8. A composition according to claim 1 in which the anionic surfactant isan ester of sulfuric acid with an aliphatic alcohol of from 10 to 18carbon atoms.
 9. A composition according to claim 1 in which the anionicsurfactant is a sulfonate having the following general formula: R-S03 Xwhere R is a straight or branched, saturated or unsaturated hydrocarbonradical having 12 to 22 carbon atoms, or an alkyl benzene having astraight or branched alkyl containing 12 to 18 carbon atoms, X is analkali metal, ammonia or alkanolamine-radical.
 10. A compositionaccording to claim 1 in which the anionic surfactant is a sulfatedalkoxylate having the following general formula: R-O-(C2H4O)nS03 X whereR is a straight or branched, saturated or unsaturated hydrocarbonradical having 8 to 22 carbon atoms, or an alkyl-substituted phenolhaving 8 to 18 carbon atoms in its alkyl portion, n is a number rangingbetween 0 and 6, and X is an alkali metal, ammonia or alkanolamineradical.
 11. A composition according to claim 1 in which the nonionicsurfactant has the following general formula: R-O-(C2H4O)nY where R is astraight or branched, saturated or unsaturated primary or secondaryalkyl radical having, in all, 8 to 26 carbon atoms, or a mono-, di- ortrialkyl-substituted phenol having, in all, 6 to 24 carbon atoms in itsalkyl portion, n is a number ranging from 1 to 50 and Y is hydrogen orthe group -(C3H6O)mH, where m is a number ranging from 1 to
 10. 12. Acomposition according to claim 1 in which the nonionic surfactant hasthe following general formula: H(OC2H4)n -(OC3H6)m -OC2-3H4-6O(C3H6O)m-(C2H4O)n where m1 and m2 are numbers ranging from 10 to 50, and n1 andn2 are numbers ranging from 1 to
 50. 13. A composition according toclaim 1 including, in addition, an alkali metal polyphosphate in anamount within the range From about 10% to about 80% by weight of thetotal solids of the composition.
 14. A composition according to claim 1including, in addition, a soil-suspending agent in an amount of fromabout 0.05% to about 5%, by weight of the total solids, selected fromalkali metal carboxymethyl cellulose, alkali metal cellulose sulphate,and lower alkyl and hydroxyalkyl cellulose ethers.
 15. A compositionaccording to claim 1, consisting essentially of 70 parts by weight ofsurfactants, 50 parts by weight sodium tripolyphosphate, 50 parts byweight sodium carbonate, 25 parts by weight sodium bicarbonate, 70 partsby weight sodium sulphate, 75 parts by weight sodium silicate, and 10parts by weight sodium carboxymethyl cellulose.
 16. A compositionaccording to claim 1, including in addition, an amount within the rangefrom about 10% to about 80% by weight of the total solids of thecomposition of an organic chelating agent selected fromaminopolycarboxylic acids and polyelectrolytes selected from the groupconsisting of polyacrylates, polyitaconates, and starch derivatives. 17.A composition according to claim 14, in which the surfactants aresulphate ester of tallow fatty alcohol adduct with 2 mols of ethyleneoxide, tallow fatty alcohol adduct with 8 mols of ethylene oxide andphosphate ester of stearyl alcohol adduct with 2.0 mols of 1,2-propyleneoxide.
 18. A composition according to claim 15, in which the surfactantsare dodecylbenzene sulphonate, tallow fatty alcohol adduct with 8 molsof ethylene oxide and phosphate ester of cetyl alcohol adduct with 2mols of 1,2-propylene oxide.
 19. A composition according to claim 15, inwhich the surfactants are C15-C18 -olefin sulphonate, tallow fattyalcohol adduct with 8 mols of ethylene oxide and phosphate ester oftallow fatty alcohol adduct with 1.2 mols of ethylene oxide.
 20. Acomposition according to claim 15, in which the surfactants are sulphateester of n-primary C12-C18 fatty alcohol and C8-C18 alcoholsulphosuccinate (1:1); tridecyl alcohol adduct with 8 mols of ethyleneoxide and phosphate ester of lauryl alcohol adduct with 2 mols ofethylene oxide.
 21. A composition according to claim 1, consistingessentially of 70 parts by weight of surfactants, 50 parts by weightsodium tripolyphosphate, 100 parts by weight trisodium nitrilotriaceticacid, 50 parts by weight sodium carbonate, 25 parts by weight sodiumbicarbonate, 70 parts by weight sodium sulphate, 75 parts by weightsodium silicate, and 10 parts by weight sodium carboxymethyl cellulose.22. A composition according to claim 21, in which the surfactants aresulphate ester of tallow fatty alcohol adduct with 2 mols of ethyleneoxide, tallow fatty alcohol adduct with 8 mols of ethylene oxide andphosphate ester of stearyl alcohol adduct with 2 mols of 1,2-propyleneoxide.
 23. A composition according to claim 21, in which the surfactantsare sodium dodecyl benzene sulphonate, tallow fatty alcohol adduct with8 mols of ethylene oxide, and phosphate ester of cetyl alcohol adductwith 2 mols of 1,2-propylene oxide.
 24. A composition according to claim21, in which the surfactants are C15-C18 -olefin sulphonate, tallowfatty alcohol adduct with 8 mols of ethylene oxide and phosphate esterof tallow fatty alcohol adduct with 1.2 mols of ethylene oxide.
 25. Acomposition according to claim 1, consisting essentially of 70 parts byweight of surfactants, 300 parts by weight sodium tripolyphosphate, 30parts by weight sodium carbonate (calcined), 5 parts by weight trisodiumphosphate, and 30 parts by weight sodium metasilicate.
 26. A compositionaccording to claim 25 in which the surfactants arE sodium dodecylbenzene sulfonate, nonyl phenol adduct with 10 mols of ethylene oxideand phosphate ester of stearyl alcohol adduct with 8.5 mols of 1,2-propylene oxide.
 27. A composition according to claim 1 consistingessentially of, in addition to the surfactant, sodium carbonate(calcined).
 28. A composition according to claim 27, in which thesurfactants are sulphate ester of n-primary C16-C20 fatty alcohol adductwith 3 mols of ethylene oxide, n-primary C16-C20 fatty alcohol adductwith 30 mols of ethylene oxide, and phosphate ester of n-primary C20-C22alcohol adduct with 3 mols of ethylene oxide.